US20100317888A1 - Carbonylation process with in situ regeneration of mordenite catalyst - Google Patents
Carbonylation process with in situ regeneration of mordenite catalyst Download PDFInfo
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- US20100317888A1 US20100317888A1 US12/735,123 US73512308A US2010317888A1 US 20100317888 A1 US20100317888 A1 US 20100317888A1 US 73512308 A US73512308 A US 73512308A US 2010317888 A1 US2010317888 A1 US 2010317888A1
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- catalyst
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- regeneration
- mordenite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 85
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 55
- 230000006315 carbonylation Effects 0.000 title claims abstract description 37
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 12
- 230000008929 regeneration Effects 0.000 title claims description 113
- 238000011069 regeneration method Methods 0.000 title claims description 113
- 239000007789 gas Substances 0.000 claims abstract description 95
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 31
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 30
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 20
- 230000001172 regenerating effect Effects 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003701 inert diluent Substances 0.000 claims abstract description 13
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 43
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- 239000010457 zeolite Substances 0.000 claims description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 239000001307 helium Substances 0.000 claims description 15
- 229910052734 helium Inorganic materials 0.000 claims description 15
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- -1 dimethyl ethyl Chemical group 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229960003903 oxygen Drugs 0.000 claims 18
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 114
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000011068 loading method Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- IZDJJEMZQZQQQQ-UHFFFAOYSA-N dicopper;tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O IZDJJEMZQZQQQQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910001657 ferrierite group Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- This invention relates to a carbonylation process in which a zeolite catalyst is regenerated in-situ, and, in particular to the in-situ regeneration of mordenite in the carbonylation of methanol, dimethyl ether and/or dimethyl carbonate.
- Zeolites such as mordenite and ferrierite are known to be suitable for use as catalysts for the carbonylation of feedstocks such as methanol, dimethyl ether and dimethyl carbonate to produce the carbonylation products methyl acetate and/or acetic acid.
- EP-A-0 596 632 describes a vapour phase process for the carbonylation of methanol to produce acetic acid in the presence of a modified mordenite catalyst at high temperatures and pressures.
- WO 2005/105720 describes a process for production of a carboxylic acid and/or an ester or anhydride thereof by carbonylating an aliphatic alcohol or reactive derivative thereof with carbon monoxide in the substantial absence of halogens in the presence of a modified mordenite catalyst at a temperature in the range 250 to 600° C. and at a pressure in the range 10 to 200 bar.
- WO 2006/121778 describes a process for the production of a lower alkyl ester of a lower aliphatic carboxylic acid by carbonylating under substantially anhydrous conditions a lower alkyl ether with carbon monoxide in the presence of a mordenite or ferrierite catalyst.
- U.S. Pat. No. 4,612,387 describes a method for making monocarboxylic acids and esters comprising contacting carbon monoxide and a monohydric alcohol containing 1 to 4 carbon atoms in the presence of a crystalline aluminosilicate zeolite having a silica to alumina ratio at least about 6 and a constraint index within the approximate range of 1 to 12 under a pressure of at least one atmosphere.
- Heterogeneous catalysts for the direct, halide-free carbonylation of methanol by Ellis et al, Studies in Surface Science and Catalysis, Vol. 111, pages 771-779, 1996, describes the catalyst preparation, performance and physical characterisation of Cu-mordenite compared to H-mordenite.
- mordenite is a highly effective carbonylation catalyst, it has been found that it undergoes deactivation with time during the carbonylation reaction. Without wishing to be bound by theory, it is believed that loss in activity and/or selectivity is at least partly due to the formation of hydro carbonaceous deposits (coke) which prevent access to the catalytically active sites of the zeolite.
- hydro carbonaceous deposits coke
- catalyst activity may be at least partially restored whilst maintaining selectivity to the desired acetyls products by treating a deactivated mordenite zeolite catalyst with a molecular oxygen-containing gas at low temperatures.
- the present invention provides a process for the production of at least one of methyl acetate and acetic acid by the carbonylation in a reactor of a carbonylatable reactant selected from methanol, dimethyl ether and dimethyl carbonate with carbon monoxide in the presence of a mordenite zeolite catalyst in which process the catalyst is regenerated in-situ by contacting the catalyst with a regenerating gas comprising a molecular oxygen-containing gas and an inert diluent at a total pressure in the range 1 to 100 bar and wherein the partial pressure of the molecular oxygen-containing gas is such that the temperature of the catalyst is maintained in the range 225 to 325° C.
- a carbonylatable reactant selected from methanol, dimethyl ether and dimethyl carbonate with carbon monoxide
- a mordenite zeolite catalyst in which process the catalyst is regenerated in-situ by contacting the catalyst with a regenerating gas comprising a molecular oxygen-containing gas and an in
- the zeolite to be regenerated in the carbonylation process of the present invention is mordenite.
- Mordenite is known to catalyse the carbonylation of methanol, dimethyl ether or dimethyl carbonate with carbon monoxide to produce at least one of methyl acetate and acetic acid.
- the structural and topological details of mordenite are well-known and are detailed in, for example, the Atlas of Zeolite Framework Types (C. Baerlocher, W. M. Meier, D. H. Olson, 5 th ed. Elsevier, Amsterdam, 2001) and its web-based version at (http://www.iza-structure.org/databases/).
- Mordenite in the hydrogen form has elliptical 6.5 ⁇ 7.0 Angstrom channels (12 member rings with window openings running in the crystallographical c-direction). It also has a system of smaller channels running perpendicular to the 12 member ring channels (and running in the b-direction). These small channels consist of 3.4 ⁇ 4.8 Angstrom channels having 8 member ring windows of these dimensions.
- the mordenite structure also possesses a zig-zag Y-branching of the pore structure due to twisted 8 member rings (in the crystallographic c-direction) this results in a distorted window to each side of the Y-branching of 2.6 ⁇ 5.7 Angstroms.
- the mordenite for use in the present invention has a silica:X 2 O 3 molar ratio of at least 5, for example, 5 to 90:1, wherein X is selected from aluminium, boron, iron, gallium and mixtures thereof.
- X will be aluminium except where framework aluminium atoms have been replaced by one or more of boron, iron and gallium.
- the mordenite zeolite will have a silica:alumina molar ratio in the range 6 to 90:1, such as 10 to 40:1.
- Mordenite is available from commercial sources, generally in the Na, NH 4 form or H-form of the mordenite.
- the NH 4 form of mordenite can be converted to the acid form (H-form) by known techniques, such as calcination at high temperature.
- the Na form of mordenite can be converted to the acid form (H-form) by converting first to an NH 4 form by ion exchange with ammonium salts such as ammonium nitrate.
- mordenite may be synthesised using known techniques.
- the mordenite may be employed in the acid form (H-form) or it may be optionally ion-exchanged or otherwise loaded with one or more metals such as copper, silver, gold, nickel, iridium, rhodium, platinum, palladium or cobalt, preferably, at least one of copper and silver.
- the metal loading on the mordenite may be expressed in terms of the fractional loading of the metal as gram atoms of metal per gram atom of aluminium in the mordenite.
- the metal loading can also be expressed as a mole percentage loading relative to aluminium in the mordenite through the relationship:
- a loading of 0.55 gram atoms of copper per aluminium in the mordenite equates to a 55 mol % loading of copper relative to aluminium in the mordenite.
- the metal loading may be in the range of 1 to 200 mol % relative to aluminium, for example, 5 to 120 mol %, such as 5 to 110 mol %.
- the mordenite catalyst is contacted with a regenerating gas comprising a molecular oxygen-containing gas and an inert diluent.
- the molecular oxygen-containing gas may be molecular oxygen, air or a gas richer or poorer in molecular oxygen than air.
- the molecular oxygen-containing gas is used in diluted form by diluting with any suitable inert diluent, for example nitrogen, helium, argon, carbon dioxide or a mixture thereof, such as a mixture of nitrogen and helium or a mixture of nitrogen and carbon dioxide.
- suitable inert diluent for example nitrogen, helium, argon, carbon dioxide or a mixture thereof, such as a mixture of nitrogen and helium or a mixture of nitrogen and carbon dioxide.
- the regenerating gas may comprise oxygen and an inert diluent selected from nitrogen, carbon dioxide and mixtures thereof.
- the regenerating gas may comprise air and an inert diluent selected from nitrogen, carbon dioxide and mixtures thereof.
- the catalyst is contacted with a pre-mixed feed of the molecular oxygen-containing gas and the inert diluent.
- the concentration of the molecular oxygen-containing gas is preferably kept low to prevent reaction exotherms and/or damage to the catalyst.
- the concentration of the molecular oxygen-containing gas, such as oxygen or air, in the regenerating gas may be in the range 0.1 mol % to 25 mol %, such as 0.5 to 20 mol % based on the total of the concentration of the molecular oxygen-containing gas and the concentration of the inert diluent.
- the concentration of the molecular oxygen-containing gas in the regenerating gas may be increased to enhance the removal of coke.
- the partial pressure of the molecular oxygen-containing gas is such that the temperature of the catalyst is maintained in the range 225 to 325° C. to at least substantially maintain the selectivity to acetyls product compared to the selectivity achieved immediately prior to regeneration.
- the temperature of a catalyst bed can be determined using known techniques, for example, by using thermocouples. Thermocouples can be placed along a catalyst bed to determine the temperature profile of the catalyst bed. The amount of molecular oxygen-containing gas entering the reactor can then be controlled so as to maintain the catalyst bed in the temperature range of 225 to 325° C.
- the partial pressure of the molecular oxygen-containing gas may be, for example, less than 1.5 bar and preferably less than 1.0 bar, for example, 0.05 to 2, such as in the range 0.05 bar to 1.5 bar or 0.18 to 1.4 bar.
- the regeneration is carried out at a catalyst temperature in the range 225 to 325° C., preferably in the range 250 to 300° C.
- the regeneration is carried out at a total pressure in the range 1 to 100 bar, such as 1 to 80 bar.
- the regeneration is carried out at a catalyst temperature in the range 250 to 300° C. and at a total pressure in the range 1 to 80 bar.
- the partial pressure of the molecular oxygen-containing gas may be adjusted. Additionally or alternatively, the temperature may be adjusted. For example, during the course of a single generation, the partial pressure of the molecular oxygen-containing gas may be increased, the temperature of the catalyst may be increased or both the catalyst temperature and partial pressure of the molecular oxygen-containing gas may be increased. Where the partial pressure of the molecular oxygen-containing gas is adjusted and/or the temperature is adjusted during a regeneration, the adjustment should not be such that the temperature of the catalyst falls outside the temperature range of 225 to 325° C.
- the gas hourly space velocity (GHSV) of the regeneration gas may suitably be in the range 500 to 10,000 h ⁇ 1 .
- the period over which the catalyst is contacted with the regenerating gas is chosen such that activity of the catalyst is greater than the activity immediately prior to the start of the regeneration process.
- the contact period is in the order of hours, such as in the range 1 to 100 hours.
- the regeneration of the catalyst is conducted ‘in-situ’.
- in-situ is meant that a carbonylation reaction is ceased, the regeneration process is carried out and then the carbonylation reaction is restarted. In this manner, it is not necessary to remove the catalyst from the carbonylation reactor.
- the carbonylatable reactant, carbon monoxide, and where used, hydrogen, feeds to the reactor are ceased.
- the reactor may be purged with an inert gas, such as nitrogen and/or helium to remove volatile components such as carbon monoxide, hydrogen, methyl acetate, light hydrocarbons and dimethyl ether contained therein.
- an inert gas such as nitrogen and/or helium to remove volatile components such as carbon monoxide, hydrogen, methyl acetate, light hydrocarbons and dimethyl ether contained therein.
- the temperature of the catalyst bed is adjusted to the required temperature by any suitable means such as by heat exchange. The temperature is adjusted so that the temperature of the catalyst is in the range 225 to 325° C.
- the regenerating gas comprising the molecular oxygen containing gas and an inert diluent is introduced into the reactor and contacted with the catalyst for a period of time to effect regeneration of the catalyst to restore catalytic activity and/or selectivity by removing hydrocarbon deposits from the catalyst after which time the regeneration is terminated.
- the reactor may be purged with an inert gas to remove molecular oxygen-containing gas remaining in the reactor. Contact of the catalyst with the carbonylatable reactant, carbon monoxide and, optionally, hydrogen may then be resumed.
- Catalyst regeneration may be performed once over the course of a carbonylation process or it may be repeated one or more times, such as four times, without significantly affecting the catalyst's performance.
- the catalyst may be regenerated in a first regeneration and then subjected to at least one subsequent, such as at least two subsequent regenerations, for example, up to four subsequent regenerations, during the course of the carbonylation process.
- catalyst regeneration may be carried out 1 to 5 times over the course of a carbonylation process.
- Each regeneration may be carried out under the same or different regeneration conditions.
- the first regeneration may be carried out under a different catalyst temperature and/or partial pressure of the molecular oxygen-containing gas to that employed in a subsequent regeneration.
- a first regeneration may be carried out at a lower temperature than a subsequent regeneration or a subsequent regeneration may be carried out at a higher molecular oxygen-containing gas partial pressure than the first regeneration.
- the first regeneration may be carried out at the same catalyst temperature and/or partial pressure of the molecular oxygen-containing gas to that employed in a subsequent regeneration.
- a subsequent regeneration may be carried out at a higher catalyst temperature than that employed in the first or a previous regeneration.
- a subsequent regeneration may also be carried out using a higher partial pressure of molecular oxygen-containing gas than that employed in the first or a previous regeneration.
- the regeneration is carried out in-situ in the production of at least one of methyl acetate and acetic acid by the carbonylation of a carbonylatable reactant selected from dimethyl ether, dimethyl carbonate and methanol.
- the carbonylation process is carried out by passing the dimethyl ether or dimethyl carbonate, carbon monoxide and, where used, hydrogen through, for example, a fixed or fluidised bed of mordenite catalyst maintained at the required temperature, such as in the range 150 to 350° C., such as 250 to 350° C.
- the process is typically carried out under substantially anhydrous conditions, that is less than 2.5 wt % water in the dimethyl ether or dimethyl carbonate feed and at a total reaction pressure in the range 1 to 100 bar and a gas hourly space velocity in the range 500 to 40,000 h ⁇ 1 .
- regeneration of the catalyst may be carried out in a single regeneration using oxygen and nitrogen and wherein the oxygen partial pressure is initially 0.7 bar and is then raised to 1.4 bar.
- Catalyst regeneration may be repeated, for example 1 to 5 times.
- the carbonylation process is carried out by passing methanol, carbon monoxide and, where used, hydrogen through, for example, a fixed or fluidised bed of mordenite catalyst maintained at the required temperature, such as in the range 250 to 400° C., such as 275 to 350° C.
- the process is typically carried out at a total reaction pressure in the range 1 to 100 bar.
- the mordenite catalyst is dried prior to use.
- the mordenite may be dried, for example by heating to a temperature of 400 to 500° C.
- the mordenite catalyst is activated immediately before use in the carbonylation reaction by heating the mordenite catalyst at elevated temperature for at least one hour under flowing nitrogen, carbon monoxide, hydrogen or mixtures thereof.
- the carbon monoxide employed in the carbonylation process may be substantially pure carbon monoxide, for example, carbon monoxide typically provided by suppliers of industrial gases, or it may contain impurities that do not interfere with the conversion of the dimethyl ether to methyl acetate, such as nitrogen, helium, argon, methane and/or carbon dioxide.
- the carbonylation process of the present invention may be conducted in the presence of hydrogen.
- the carbon monoxide feed may contain hydrogen.
- Mixtures of hydrogen and carbon monoxide are commercially produced by the steam reforming of hydrocarbons and by the partial oxidation of hydrocarbons. Such mixtures are commonly referred to as synthesis gas.
- Synthesis gas comprises mainly carbon monoxide and hydrogen but may also contain smaller quantities of carbon dioxide.
- the molar ratio of carbon monoxide:hydrogen may be in the range 1:3 to 15:1.
- the molar ratio of carbon monoxide to dimethyl ether or dimethyl carbonate may be in the range 1:1 to 99:1.
- the molar ratio of carbon monoxide to methanol is suitably in the range 1:1 to 60:1.
- the carbonylation process may be conducted as a batch or as a continuous process, preferably as a continuous process.
- FIG. 1 depicts the STY to methyl acetate product in g kg ⁇ 1 h ⁇ 1 versus time on stream for H-mordenite and Cu-mordenite catalysts before and after 2 regenerations at 300° C.
- FIG. 2 depicts Selectivity to methyl acetate product versus time on stream for Cu-mordenite before and after 2 regenerations at 300° C.
- FIG. 3 depicts the STY to methyl acetate product in g kg ⁇ 1 h ⁇ 1 versus time on stream for Cu-mordenite and H-mordenite before and after 2 regenerations at 250° C. and a 3 rd regeneration at 300° C.
- FIG. 4 depicts Selectivity to methyl acetate product versus time on stream for Cu-mordenite and H-mordenite before and after 2 regenerations at 250° C. and a 3 rd regeneration at 300° C.
- FIG. 5 depicts the STY to methyl acetate product in g kg ⁇ 1 h ⁇ 1 versus time on stream for Ag-mordenite before and after 4 regenerations at 250° C.
- FIG. 6 depicts Selectivity to methyl acetate product versus time on stream for Ag-mordenite before and after 4 regenerations at 250° C.
- FIG. 7 depicts the STY to acetyls product in g l ⁇ 1 h ⁇ 1 versus time on stream for Cu-mordenite before and after regeneration at 250° C., 300° C., 350° C. and 400° C.
- FIG. 8 depicts Selectivity to acetyls product versus time on stream for Cu-mordenite before and after regeneration at 250° C., 300° C., 350° C. and 400° C.
- FIG. 9 depicts Selectivity to acetyls product versus time on stream for Ag-mordenite before and after regeneration at 250° C., 300° C., 350° C. and 400° C.
- FIG. 10 depicts Selectivity to acetyls product versus time on stream for H-mordenite before and after regeneration at 250° C., 300° C. and 400° C.
- the temperature was ramped to 300° C. at 0.5° C./min, again followed by a further dwell time of 3 hours.
- the gas feed was then switched to a mixture of carbon monoxide hydrogen and DME with a CO/H 2 /DME ratio of 72/18/10 at a flow rate of 4 l/h, with the DME fed at 0.38 l/h as a vapour, to obtain a CO/H 2 /DME ratio in the total feed of 72/18/10 on a molar basis.
- N 2 was introduced at a variable rate of 0-50 ml/min to equalise the pressure swings between the 16 reactor exits.
- the exit stream from each test reactor was passed to a gas chromatograph to determine the concentration of reactants and carbonylation products.
- H-mordenite (100.1 g) with a silica to alumina ratio of 20 (ex Süd-Chemie) was weighed into a 1 litre round bottomed flask with a stirrer bar. 18.1 g of copper (II) nitrate hemipentahydrate (98% ACS reagent grade) was dissolved in a minimum amount of deionised water. This solution was then added to the mordenite together with sufficient deionised water (ca. 150 mL) to give a mobile slurry. The top of the flask was covered loosely and the flask left to stir overnight. The zeolite was then dried under reduced vacuum using a rotary evaporator before being dried in an oven at 90° C. for 1-2 hours.
- the zeolite (ca. 0.75 g batches) was then compacted at 10 tonnes in a 13 mm die set using a pneumatic press, and crushed and sieved to a particle size fraction of 125 to 160 microns.
- the zeolite (Cu(55)-Mordenite) had a Cu loading of ca. 55 mole % relative to Al contained in the mordenite
- the zeolite was then compacted (ca. 0.75 g at a time) at 10 tonnes in a 13 mm die set using a pneumatic press, and crushed and sieved to a particle size fraction of 125 to 160 microns.
- the DME carbonylation reaction was then re-started under conditions of 300° C., 70 bar total pressure, a GHSV of 4000 h ⁇ 1 with a feedstock ratio of CO/H 2 /DME 72/18/10.
- the reaction was then allowed to continue for a further 53 hours (172 hours total) and the CO/H 2 /DME feed was switched to N 2 and the reactors purged for 30 minutes.
- the catalyst was then subjected to a second regeneration using the same procedure as in the first regeneration.
- the DME carbonylation reaction was then re-started under conditions of 300° C., 70 bar, a GHSV of 4000 h ⁇ 1 with a feedstock ratio of CO/H 2 /DME 72/18/10. The reaction was then allowed to continue for a further 64 hours.
- FIG. 1 shows the initial carbonylation activity of the H-Mordenite catalyst to be fully restored after treatment with 1 volume % (0.7 bar) and 2 volume % (1.4 bar) O 2 at 300° C.
- FIG. 1 also shows the initial carbonylation activity of the Cu(55)-Mordenite catalyst to be largely restored after treatment with 1 and 2 volume % O 2 at 300° C.
- FIG. 2 shows the initial selectivity of the Cu(55)-Mordenite catalyst to MeOAc (based upon DME converted) to be restored to its original level after regeneration of the catalyst with 1 and 2 volume % (0.7 and 1.4 bar respectively) O 2 at 300° C.
- a Cu(55) mordenite and H-mordenite prepared as described above were used as the catalyst in Examples 3 and 4 respectively.
- Each catalyst was used in the carbonylation of dimethyl ether to prepare methyl acetate by the procedure described in General Reaction Method 1 except that the carbon monoxide, hydrogen, dimethyl ether gas feed had a molar ratio of 76/19/5 and a flow rate of 4 l/h, with a dimethyl ether flow rate of 0.196 l/h (as a vapour) to obtain a CO/H 2 /DME ratio in the total feed of 76/19/5 on a molar basis.
- the reaction was allowed to continue for 123 hours under conditions of 300° C., 70 bar total pressure, a GHSV of 4000 h ⁇ 1 and a CO/H 2 /DME ratio in the total feed of 76/19/5 on a molar basis.
- the CO/H 2 /DME feed was switched to N 2 and the reactors purged for 30 minutes.
- the temperature of the reactors was dropped to 250° C. and each catalyst was subjected to a first regeneration as follows:
- the catalysts were regenerated at 250° C. and 70 bar total pressure with a gas stream containing 1 volume % (0.7 bar) O 2 and 99 volume % N 2 for 13.5 hours at a GHSV of 4000 h ⁇ 1 .
- the O 2 content in the gas stream was then increased to 2 volume % (1.4 bar) (with 98 volume % N 2 ) and the catalysts were treated for a further 4 hours at 70 bar total pressure and 250° C.
- the reactors were purged for 30 minutes with N 2 and then heated at 3° C./min to 300° C.
- the carbonylation reaction was then re-started under conditions of 300° C., 70 bar total pressure and a GHSV of 4000 h ⁇ 1 with a CO/H 2 /DME molar ratio of 76/19/5.
- the reaction was allowed to continue for a further 48 hours (197 hours total), after which time, the CO/H 2 /DME feed was switched to N 2 and the reactors purged for 30 minutes.
- the temperature of the reactors was dropped to 250° C. and the catalysts were regenerated for a second time by repeating the procedure employed in the first regeneration.
- the reactors were purged for 30 minutes with N 2 and then heated at 3° C./min to 300° C.
- the carbonylation reaction was re-started under conditions of 300° C., 70 bar, a GHSV of 4000 with a CO/H 2 /DME molar ratio of 76/19/5.
- the reaction was allowed to continue for a further 69 hours (287 hours total reaction time) after which time, the CO/H 2 /DME feed was switched to N 2 and the reactors purged for 30 minutes.
- the temperature of the reactors was dropped to 250° C.
- the catalysts were regenerated for a third time by treating the catalysts at 300° C.
- the carbonylation reaction was re-started under conditions of 300° C., 70 bar total pressure and a GHSV of 4000 h ⁇ 1 with a CO/H 2 /DME molar ratio of 76/19/5. The reaction was allowed to continue for a further 46 hours.
- FIG. 3 shows the initial carbonylation activity of the Cu(55)-Mordenite to be fully restored after 2 regenerations of the catalyst with 1 and 2 volume % O 2 at 250° C.
- Catalyst activity data after regeneration 3 shown in FIG. 3 also illustrates that after first treating the H-Mordenite catalysts with O 2 at 250° C. it is beneficial to further treat the catalyst with O 2 at 300° C.
- FIG. 4 shows that the selectivity of the catalysts after each regeneration is improved compared to the selectivity immediately prior to regeneration.
- NH 4 -mordenite 25.05 g
- silica to alumina ratio of 20 (ex Zeolyst) was weighed into a 250 mL round bottomed flask with a stirrer bar.
- 3.2726 g of silver (I) nitrate was dissolved in a minimum amount of deionised water. This solution was then added to the mordenite along with sufficient deionised water (ca. 150 mL) to give a mobile slurry.
- the top of the flask was covered loosely and the flask stirred overnight.
- the zeolite was then dried under reduced vacuum using a rotary evaporator before being dried in an oven at 90° C. for 1-2 hours.
- the zeolite (ca. 0.75 g batches) was then compacted at 10 tonnes in a 13 mm die set using a pneumatic press, and crushed and sieved to a particle size fraction of 125 to 160 microns.
- the zeolite (Ag(55)-MOR) had a Ag loading of ca. 55 mole % relative to Al contained in the mordenite. ICP spectroscopic analysis showed the mordenite catalyst to contain 8.2% Ag and 3.6% Al on a % by weight basis, equivalent to a Ag loading of 57 mole % relative to Al.
- the reactors were purged for 30 minutes with N 2 and then heated at 3° C./min to 300° C.
- the carbonylation reaction was re-started under conditions of 300° C., 70 bar total pressure and a GHSV of 4000 h ⁇ 1 with a CO/H 2 /DME molar ratio of 72/18/10.
- the reaction was allowed to continue for a further 50 hours (171 hours total reaction time), after which time the CO/H 2 /DME feed was switched to N 2 and the reactors purged for 30 minutes.
- the temperature of the reactors was dropped to 250° C. and the catalyst was subjected to a second regeneration by repeating the method of the first regeneration.
- the reactors were again purged for 30 minutes with N 2 and then heated at 3° C./min to 300° C.
- the carbonylation reaction was re-started under conditions of 300° C., 70 bar, a GHSV of 4000 h ⁇ 1 with a CO/H 2 /DME molar ratio of 72/18/10.
- the reaction was allowed to continue for a further 71 hours (to a total of 265 hours), after which time the CO/H 2 /DME feed was switched to N 2 and the reactors purged for 30 minutes.
- After purging with N 2 the temperature of the reactors was dropped to 250° C.
- the catalyst was regenerated for a third time by repeating the method of the first regeneration.
- the reactors were purged for 30 minutes with N 2 and then heated at 3° C./min to 300° C.
- the carbonylation reaction was re-started under conditions of 300° C., 70 bar, a GHSV of 4000 with a CO/H 2 /DME molar ratio of 72/18/10.
- the reaction was allowed to continue for a further 48 hours (to 339 hours total reaction time), after which time, the CO/H 2 /DME feed was switched to N 2 and the reactors purged for 30 minutes.
- the temperature of the reactors was dropped to 250° C. and the catalyst was regenerated for a fourth time by repeating the method of the first regeneration.
- the reactors were purged for 30 minutes with N 2 and then heated at 3° C./min to 300° C.
- the carbonylation reaction was re-started under conditions of 300° C., 70 bar, a GHSV of 4000 h ⁇ 1 with a CO/H 2 /DME molar ratio of 72/18/10. The reaction was then allowed to continue for a further 69 hours.
- FIGS. 5 and 6 show the results for Example 5 .
- FIG. 5 shows the initial carbonylation activity of the Ag(55)-Mordenite catalyst to be substantially restored after the first regeneration of the catalyst with 1 and 2 volume % O 2 at 250° C.
- FIG. 6 shows that the selectivity of the catalyst after each regeneration is maintained at or above the selectivity achieved immediately prior to each regeneration.
- H-Mordenite 80 g with a silica to alumina ratio of 20 (ex Süd Chemie) and 14.29 g of copper (II) nitrate hemipentahydrate (98% ACS reagent grade) were weighed into a 500 mL round bottomed flask with a stirrer bar. Sufficient deionised water (ca. 150 mL) was added to the flask to obtain a thick slurry. The top of the flask was loosely covered and the flask left to stir overnight. The zeolite was then dried under reduced vacuum using a rotary evaporator before being dried in an oven at 90° C. for 1 hour.
- Ag-mordenite was prepared by the procedure as described above for the preparation of Cu-mordenite except that the copper (II) nitrate was replaced by 10.47 g of silver nitrate (99% ACS reagent grade).
- the Ag-mordenite so prepared had a Ag loading of 55 mole % of the amount of Al contained in the mordenite.
- H-Mordenite 80 g
- silica to alumina ratio 20 (ex Süd Chemie) was calcined, compacted, crushed and sieved in accordance with the procedures described in the preparation of Cu-mordenite above.
- Each of the catalysts, Cu-mordenite, Ag-mordenite and H-mordenite was used to catalyse the carbonylation of dimethyl ether to methyl acetate using the following apparatus and procedure.
- the carbonylation reaction was carried out in a pressure flow reactor unit consisting of 60 identical parallel isothermal co-current tubular reactors of the type described in, for example, WO2006107187.
- the reactors were arranged in 4 blocks of 15 reactors, each block having an independent temperature control.
- 50 micro litres of catalyst (designed to give a GHSV of 4000 hr ⁇ 1 ) was loaded onto a metal sinter having a pore size of 20 micrometers.
- the catalyst samples were heated at a ramp rate of 5° C./min.
- Block Nitrogen Air* Helium 1 deg Block 2 Block 3 Block 4 Time mole % mole % mole % mole % C. deg C. deg C. deg C. hours 78.9 19.7 1.4 250 300 350 400 5.8 59.2 39.4 1.4 250 300 350 400 5.8 19.7 78.9 1.4 250 300 350 400 5.8 *Air 20.95 mol % oxygen, 78.05 mol % nitrogen and 1 mol % other gases, mostly argon.
- the gas feed was changed to a mixture comprising 98.6 mole % nitrogen and 1.4% helium and the reactor were allowed to cool down to 100° C.
- the system was held at this condition for 30 minutes before the reactors were heated to 300° C. and the gas feed changed to a mixture comprising 63.1 mole % carbon monoxide, 15.8 mole % hydrogen, 19.7 mole % nitrogen and 1.4 mole % helium at a gas flow rate of 3.4 mL/min.
- the system was held at this condition for 3 hours before the carbonylation reaction was re-started by changing the feed to a mixture comprising 63.1 mole % carbon monoxide, 15.8 mole % hydrogen, 14.8 mole % nitrogen, 1.4 mole % helium and 4.9 mole % dimethyl ether.
- the exit stream from the reactor was passed to two gas chromatographs.
- One of these was a Varian 4900 micro GC with three columns (Molecular sieve 5 A, Porapak® Q, and CP-Wax-52) each quipped with a thermal conductivity detector.
- the other was an Interscience Trace GC with two columns (CP-Sil 5 and CP-Wax 52) each equipped with a flame ionisation detector.
- the STY to Acetyls products (g/l/h) is shown in FIG. 7 and Selectivity to Acetyls products is shown in FIGS. 8 to 10 .
- Selectivity is defined as the molar selectivity of the reaction of the methoxy group in the dimethyl ether (DME) feed to the products acetic acid (AcOH) and methyl acetate (MeOAc).
- FIG. 7 shows that the activity of the Cu-mordenite catalyst is restored after regeneration.
- FIG. 8 shows that shortly after regeneration at 250 and 300° C. the selectivity of Cu-mordenite catalyst has been substantially restored to the selectivity achieved immediately prior to regeneration. In comparison the selectivity of Cu-mordenite regenerated at 350 and 400° C. has been dramatically reduced, and even though the selectivity of the catalyst regenerated at 350° C. is recovering it is still not within 10% of the selectivity of the catalyst prior to the regeneration treatment after over 60 hours of operation.
- FIG. 9 shows that regeneration at 350° C. and 400° C. adversely affects the selectivity of the Ag-mordenite catalyst and
- FIG. 10 shows that regeneration at 400° C. adversely affects the selectivity of the H-mordenite catalyst.
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Abstract
Description
- This invention relates to a carbonylation process in which a zeolite catalyst is regenerated in-situ, and, in particular to the in-situ regeneration of mordenite in the carbonylation of methanol, dimethyl ether and/or dimethyl carbonate.
- Zeolites, such as mordenite and ferrierite are known to be suitable for use as catalysts for the carbonylation of feedstocks such as methanol, dimethyl ether and dimethyl carbonate to produce the carbonylation products methyl acetate and/or acetic acid.
- EP-A-0 596 632 describes a vapour phase process for the carbonylation of methanol to produce acetic acid in the presence of a modified mordenite catalyst at high temperatures and pressures.
- WO 2005/105720 describes a process for production of a carboxylic acid and/or an ester or anhydride thereof by carbonylating an aliphatic alcohol or reactive derivative thereof with carbon monoxide in the substantial absence of halogens in the presence of a modified mordenite catalyst at a temperature in the
range 250 to 600° C. and at a pressure in therange 10 to 200 bar. - WO 2006/121778 describes a process for the production of a lower alkyl ester of a lower aliphatic carboxylic acid by carbonylating under substantially anhydrous conditions a lower alkyl ether with carbon monoxide in the presence of a mordenite or ferrierite catalyst.
- U.S. Pat. No. 4,612,387 describes a method for making monocarboxylic acids and esters comprising contacting carbon monoxide and a monohydric alcohol containing 1 to 4 carbon atoms in the presence of a crystalline aluminosilicate zeolite having a silica to alumina ratio at least about 6 and a constraint index within the approximate range of 1 to 12 under a pressure of at least one atmosphere.
- ‘Heterogeneous catalysts for the direct, halide-free carbonylation of methanol’ by Ellis et al, Studies in Surface Science and Catalysis, Vol. 111, pages 771-779, 1996, describes the catalyst preparation, performance and physical characterisation of Cu-mordenite compared to H-mordenite.
- However, although mordenite is a highly effective carbonylation catalyst, it has been found that it undergoes deactivation with time during the carbonylation reaction. Without wishing to be bound by theory, it is believed that loss in activity and/or selectivity is at least partly due to the formation of hydro carbonaceous deposits (coke) which prevent access to the catalytically active sites of the zeolite. Thus, there remains a need for a method for treating a deactivated mordenite zeolite catalyst, in-situ, in order to at least partially restore activity whilst maintaining selectivity to acetyls products.
- It has now been found that catalyst activity may be at least partially restored whilst maintaining selectivity to the desired acetyls products by treating a deactivated mordenite zeolite catalyst with a molecular oxygen-containing gas at low temperatures.
- Accordingly, the present invention provides a process for the production of at least one of methyl acetate and acetic acid by the carbonylation in a reactor of a carbonylatable reactant selected from methanol, dimethyl ether and dimethyl carbonate with carbon monoxide in the presence of a mordenite zeolite catalyst in which process the catalyst is regenerated in-situ by contacting the catalyst with a regenerating gas comprising a molecular oxygen-containing gas and an inert diluent at a total pressure in the
range 1 to 100 bar and wherein the partial pressure of the molecular oxygen-containing gas is such that the temperature of the catalyst is maintained in therange 225 to 325° C. - The zeolite to be regenerated in the carbonylation process of the present invention is mordenite. Mordenite is known to catalyse the carbonylation of methanol, dimethyl ether or dimethyl carbonate with carbon monoxide to produce at least one of methyl acetate and acetic acid. The structural and topological details of mordenite are well-known and are detailed in, for example, the Atlas of Zeolite Framework Types (C. Baerlocher, W. M. Meier, D. H. Olson, 5th ed. Elsevier, Amsterdam, 2001) and its web-based version at (http://www.iza-structure.org/databases/). These compendia provide structural information on all zeolite framework types which have been approved by the Structure Commission of the International Zeolite Association. Mordenite in the hydrogen form has elliptical 6.5×7.0 Angstrom channels (12 member rings with window openings running in the crystallographical c-direction). It also has a system of smaller channels running perpendicular to the 12 member ring channels (and running in the b-direction). These small channels consist of 3.4×4.8 Angstrom channels having 8 member ring windows of these dimensions. The mordenite structure also possesses a zig-zag Y-branching of the pore structure due to twisted 8 member rings (in the crystallographic c-direction) this results in a distorted window to each side of the Y-branching of 2.6×5.7 Angstroms.
- Preferably, the mordenite for use in the present invention has a silica:X2O3 molar ratio of at least 5, for example, 5 to 90:1, wherein X is selected from aluminium, boron, iron, gallium and mixtures thereof. Generally, X will be aluminium except where framework aluminium atoms have been replaced by one or more of boron, iron and gallium. Typically, the mordenite zeolite will have a silica:alumina molar ratio in the range 6 to 90:1, such as 10 to 40:1.
- Mordenite is available from commercial sources, generally in the Na, NH4 form or H-form of the mordenite. The NH4 form of mordenite can be converted to the acid form (H-form) by known techniques, such as calcination at high temperature. The Na form of mordenite can be converted to the acid form (H-form) by converting first to an NH4 form by ion exchange with ammonium salts such as ammonium nitrate. Alternatively, mordenite may be synthesised using known techniques.
- For use as the catalyst in a carbonylation process to produce methyl acetate and/or acetic acid, the mordenite may be employed in the acid form (H-form) or it may be optionally ion-exchanged or otherwise loaded with one or more metals such as copper, silver, gold, nickel, iridium, rhodium, platinum, palladium or cobalt, preferably, at least one of copper and silver.
- The metal loading on the mordenite may be expressed in terms of the fractional loading of the metal as gram atoms of metal per gram atom of aluminium in the mordenite. The metal loading can also be expressed as a mole percentage loading relative to aluminium in the mordenite through the relationship:
-
mol % Metal=(gram atoms Metal/gram atoms aluminium)×100 - Thus, for example, a loading of 0.55 gram atoms of copper per aluminium in the mordenite equates to a 55 mol % loading of copper relative to aluminium in the mordenite.
- Suitably, the metal loading may be in the range of 1 to 200 mol % relative to aluminium, for example, 5 to 120 mol %, such as 5 to 110 mol %.
- In the process of the present invention, the mordenite catalyst is contacted with a regenerating gas comprising a molecular oxygen-containing gas and an inert diluent.
- The molecular oxygen-containing gas may be molecular oxygen, air or a gas richer or poorer in molecular oxygen than air.
- The molecular oxygen-containing gas is used in diluted form by diluting with any suitable inert diluent, for example nitrogen, helium, argon, carbon dioxide or a mixture thereof, such as a mixture of nitrogen and helium or a mixture of nitrogen and carbon dioxide.
- Suitably, the regenerating gas may comprise oxygen and an inert diluent selected from nitrogen, carbon dioxide and mixtures thereof. Alternatively, the regenerating gas may comprise air and an inert diluent selected from nitrogen, carbon dioxide and mixtures thereof.
- The catalyst is contacted with a pre-mixed feed of the molecular oxygen-containing gas and the inert diluent.
- The concentration of the molecular oxygen-containing gas is preferably kept low to prevent reaction exotherms and/or damage to the catalyst. Suitably, the concentration of the molecular oxygen-containing gas, such as oxygen or air, in the regenerating gas may be in the range 0.1 mol % to 25 mol %, such as 0.5 to 20 mol % based on the total of the concentration of the molecular oxygen-containing gas and the concentration of the inert diluent. During the regeneration, the concentration of the molecular oxygen-containing gas in the regenerating gas may be increased to enhance the removal of coke.
- The partial pressure of the molecular oxygen-containing gas, such as air or oxygen, is such that the temperature of the catalyst is maintained in the
range 225 to 325° C. to at least substantially maintain the selectivity to acetyls product compared to the selectivity achieved immediately prior to regeneration. The temperature of a catalyst bed can be determined using known techniques, for example, by using thermocouples. Thermocouples can be placed along a catalyst bed to determine the temperature profile of the catalyst bed. The amount of molecular oxygen-containing gas entering the reactor can then be controlled so as to maintain the catalyst bed in the temperature range of 225 to 325° C. - Suitably, at a total pressure in the
range 1 to 100 bar, the partial pressure of the molecular oxygen-containing gas may be, for example, less than 1.5 bar and preferably less than 1.0 bar, for example, 0.05 to 2, such as in the range 0.05 bar to 1.5 bar or 0.18 to 1.4 bar. - The regeneration is carried out at a catalyst temperature in the
range 225 to 325° C., preferably in therange 250 to 300° C. - The regeneration is carried out at a total pressure in the
range 1 to 100 bar, such as 1 to 80 bar. - Suitably, the regeneration is carried out at a catalyst temperature in the
range 250 to 300° C. and at a total pressure in therange 1 to 80 bar. - During the regeneration, the partial pressure of the molecular oxygen-containing gas may be adjusted. Additionally or alternatively, the temperature may be adjusted. For example, during the course of a single generation, the partial pressure of the molecular oxygen-containing gas may be increased, the temperature of the catalyst may be increased or both the catalyst temperature and partial pressure of the molecular oxygen-containing gas may be increased. Where the partial pressure of the molecular oxygen-containing gas is adjusted and/or the temperature is adjusted during a regeneration, the adjustment should not be such that the temperature of the catalyst falls outside the temperature range of 225 to 325° C.
- The gas hourly space velocity (GHSV) of the regeneration gas may suitably be in the
range 500 to 10,000 h−1. - The period over which the catalyst is contacted with the regenerating gas is chosen such that activity of the catalyst is greater than the activity immediately prior to the start of the regeneration process. Typically, the contact period is in the order of hours, such as in the
range 1 to 100 hours. - The regeneration of the catalyst is conducted ‘in-situ’. By ‘in-situ’ is meant that a carbonylation reaction is ceased, the regeneration process is carried out and then the carbonylation reaction is restarted. In this manner, it is not necessary to remove the catalyst from the carbonylation reactor.
- To carry out the regeneration in-situ, the carbonylatable reactant, carbon monoxide, and where used, hydrogen, feeds to the reactor are ceased. In addition, to prevent potential safety hazards, prior to introducing the molecular oxygen-containing gas used for the regeneration, the reactor may be purged with an inert gas, such as nitrogen and/or helium to remove volatile components such as carbon monoxide, hydrogen, methyl acetate, light hydrocarbons and dimethyl ether contained therein. Where the carbonylation reaction is carried out at temperature which is different to that used for the regenerating procedure, the temperature of the catalyst bed is adjusted to the required temperature by any suitable means such as by heat exchange. The temperature is adjusted so that the temperature of the catalyst is in the
range 225 to 325° C. Once the catalyst bed is at the required temperature, the regenerating gas comprising the molecular oxygen containing gas and an inert diluent is introduced into the reactor and contacted with the catalyst for a period of time to effect regeneration of the catalyst to restore catalytic activity and/or selectivity by removing hydrocarbon deposits from the catalyst after which time the regeneration is terminated. After terminating the regeneration process, the reactor may be purged with an inert gas to remove molecular oxygen-containing gas remaining in the reactor. Contact of the catalyst with the carbonylatable reactant, carbon monoxide and, optionally, hydrogen may then be resumed. - Catalyst regeneration may be performed once over the course of a carbonylation process or it may be repeated one or more times, such as four times, without significantly affecting the catalyst's performance. The catalyst may be regenerated in a first regeneration and then subjected to at least one subsequent, such as at least two subsequent regenerations, for example, up to four subsequent regenerations, during the course of the carbonylation process. Suitably, catalyst regeneration may be carried out 1 to 5 times over the course of a carbonylation process. Each regeneration may be carried out under the same or different regeneration conditions. Suitably, where the regeneration is repeated, the first regeneration may be carried out under a different catalyst temperature and/or partial pressure of the molecular oxygen-containing gas to that employed in a subsequent regeneration. For example, a first regeneration may be carried out at a lower temperature than a subsequent regeneration or a subsequent regeneration may be carried out at a higher molecular oxygen-containing gas partial pressure than the first regeneration.
- Alternatively, the first regeneration may be carried out at the same catalyst temperature and/or partial pressure of the molecular oxygen-containing gas to that employed in a subsequent regeneration. For example, a subsequent regeneration may be carried out at a higher catalyst temperature than that employed in the first or a previous regeneration. A subsequent regeneration may also be carried out using a higher partial pressure of molecular oxygen-containing gas than that employed in the first or a previous regeneration.
- The regeneration is carried out in-situ in the production of at least one of methyl acetate and acetic acid by the carbonylation of a carbonylatable reactant selected from dimethyl ether, dimethyl carbonate and methanol.
- Where dimethyl ether or dimethyl carbonate is used as the carbonylatable reactant, the carbonylation process is carried out by passing the dimethyl ether or dimethyl carbonate, carbon monoxide and, where used, hydrogen through, for example, a fixed or fluidised bed of mordenite catalyst maintained at the required temperature, such as in the
range 150 to 350° C., such as 250 to 350° C. The process is typically carried out under substantially anhydrous conditions, that is less than 2.5 wt % water in the dimethyl ether or dimethyl carbonate feed and at a total reaction pressure in therange 1 to 100 bar and a gas hourly space velocity in therange 500 to 40,000 h−1. - Suitably, in the carbonylation of dimethyl ether using H-mordenite or a metal loaded mordenite such as a copper or silver loaded mordenite catalyst at a total pressure of 70 bar, regeneration of the catalyst may be carried out in a single regeneration using oxygen and nitrogen and wherein the oxygen partial pressure is initially 0.7 bar and is then raised to 1.4 bar. Catalyst regeneration may be repeated, for example 1 to 5 times.
- Where methanol is used as the carbonylatable reactant, the carbonylation process is carried out by passing methanol, carbon monoxide and, where used, hydrogen through, for example, a fixed or fluidised bed of mordenite catalyst maintained at the required temperature, such as in the
range 250 to 400° C., such as 275 to 350° C. The process is typically carried out at a total reaction pressure in therange 1 to 100 bar. - If the carbonylation reaction is to be conducted substantially in the absence of water, it is preferred that the mordenite catalyst is dried prior to use. The mordenite may be dried, for example by heating to a temperature of 400 to 500° C.
- Suitably, the mordenite catalyst is activated immediately before use in the carbonylation reaction by heating the mordenite catalyst at elevated temperature for at least one hour under flowing nitrogen, carbon monoxide, hydrogen or mixtures thereof.
- The carbon monoxide employed in the carbonylation process may be substantially pure carbon monoxide, for example, carbon monoxide typically provided by suppliers of industrial gases, or it may contain impurities that do not interfere with the conversion of the dimethyl ether to methyl acetate, such as nitrogen, helium, argon, methane and/or carbon dioxide.
- The carbonylation process of the present invention may be conducted in the presence of hydrogen. Thus, the carbon monoxide feed may contain hydrogen. Mixtures of hydrogen and carbon monoxide are commercially produced by the steam reforming of hydrocarbons and by the partial oxidation of hydrocarbons. Such mixtures are commonly referred to as synthesis gas. Synthesis gas comprises mainly carbon monoxide and hydrogen but may also contain smaller quantities of carbon dioxide. The molar ratio of carbon monoxide:hydrogen may be in the range 1:3 to 15:1. The molar ratio of carbon monoxide to dimethyl ether or dimethyl carbonate may be in the range 1:1 to 99:1. The molar ratio of carbon monoxide to methanol is suitably in the range 1:1 to 60:1.
- The carbonylation process may be conducted as a batch or as a continuous process, preferably as a continuous process.
- In the Figures,
FIG. 1 depicts the STY to methyl acetate product in g kg−1 h−1 versus time on stream for H-mordenite and Cu-mordenite catalysts before and after 2 regenerations at 300° C. -
FIG. 2 depicts Selectivity to methyl acetate product versus time on stream for Cu-mordenite before and after 2 regenerations at 300° C. -
FIG. 3 depicts the STY to methyl acetate product in g kg−1 h−1 versus time on stream for Cu-mordenite and H-mordenite before and after 2 regenerations at 250° C. and a 3rd regeneration at 300° C. -
FIG. 4 depicts Selectivity to methyl acetate product versus time on stream for Cu-mordenite and H-mordenite before and after 2 regenerations at 250° C. and a 3rd regeneration at 300° C. -
FIG. 5 depicts the STY to methyl acetate product in g kg−1 h−1 versus time on stream for Ag-mordenite before and after 4 regenerations at 250° C. -
FIG. 6 depicts Selectivity to methyl acetate product versus time on stream for Ag-mordenite before and after 4 regenerations at 250° C. -
FIG. 7 depicts the STY to acetyls product in g l−1 h−1 versus time on stream for Cu-mordenite before and after regeneration at 250° C., 300° C., 350° C. and 400° C. -
FIG. 8 depicts Selectivity to acetyls product versus time on stream for Cu-mordenite before and after regeneration at 250° C., 300° C., 350° C. and 400° C. -
FIG. 9 depicts Selectivity to acetyls product versus time on stream for Ag-mordenite before and after regeneration at 250° C., 300° C., 350° C. and 400° C. -
FIG. 10 depicts Selectivity to acetyls product versus time on stream for H-mordenite before and after regeneration at 250° C., 300° C. and 400° C. - The invention is now illustrated with reference to the following Examples.
- The carbonylation of dimethyl ether (DME) in the presence of a mordenite zeolite catalyst was carried out in a pressure flow reactor unit consisting of 16 identical reactors of the type described in WO 2005063372. Prior to the loading of a catalyst sample into the reactor, a ca. 5 cm bed of steatite of sieve fraction of 100-350 μm was placed in the respective catalyst sample holder. A ca. 5 cm zone of corundum of sieve fraction of 125-160 μm was placed on top of the steatite bed. On a dry mass basis (determined by loss on ignition of the relevant sample measured by heating the sample from room temperature to 600° C. at a ramp rate of ca. 30° C. per minute) a 0.625 g (ca. 1 ml) sample of a catalyst was then placed on top of the corundum bed. The catalyst sample was covered by a ca. 5 cm corundum bed of a particle size of 125-160 μm. A ca. 5 cm zone of steatite of sieve fraction of 100-350 μm was placed on top of the corundum bed. Every zone was concreted via hitting or vibrating to get a stable bed and a defined starting height of the catalyst zone. The catalyst sample was then pressurised to the desired reaction pressure of 70 bar with CO/
H 2 4/1 mixture at a flow rate of 4 l/h. The catalyst was then heated at 0.5° C./min to a holding temperature of 220° C., where it was held for a dwell time of 3 hours. Subsequently the temperature was ramped to 300° C. at 0.5° C./min, again followed by a further dwell time of 3 hours. The gas feed was then switched to a mixture of carbon monoxide hydrogen and DME with a CO/H2/DME ratio of 72/18/10 at a flow rate of 4 l/h, with the DME fed at 0.38 l/h as a vapour, to obtain a CO/H2/DME ratio in the total feed of 72/18/10 on a molar basis. In addition, N2 was introduced at a variable rate of 0-50 ml/min to equalise the pressure swings between the 16 reactor exits. The exit stream from each test reactor was passed to a gas chromatograph to determine the concentration of reactants and carbonylation products. - H-mordenite (100.1 g) with a silica to alumina ratio of 20 (ex Süd-Chemie) was weighed into a 1 litre round bottomed flask with a stirrer bar. 18.1 g of copper (II) nitrate hemipentahydrate (98% ACS reagent grade) was dissolved in a minimum amount of deionised water. This solution was then added to the mordenite together with sufficient deionised water (ca. 150 mL) to give a mobile slurry. The top of the flask was covered loosely and the flask left to stir overnight. The zeolite was then dried under reduced vacuum using a rotary evaporator before being dried in an oven at 90° C. for 1-2 hours. The zeolite was then calcined in a muffle oven (oven volume=18 L) under a static atmosphere of air at 500° C. for 3 hours after two drying stages of 90° C. for 2 hours and 110° C. for 2 hours. The zeolite (ca. 0.75 g batches) was then compacted at 10 tonnes in a 13 mm die set using a pneumatic press, and crushed and sieved to a particle size fraction of 125 to 160 microns. The zeolite (Cu(55)-Mordenite) had a Cu loading of ca. 55 mole % relative to Al contained in the mordenite
- H-mordenite with a silica to alumina ratio of 20 (ex Süd-Chemie) was calcined in a muffle oven (oven volume=18 L) under a static atmosphere of air at 500° C. for 3 hours after two drying stages of 90° C. for 2 hours and 110° C. for 2 hours. The zeolite was then compacted (ca. 0.75 g at a time) at 10 tonnes in a 13 mm die set using a pneumatic press, and crushed and sieved to a particle size fraction of 125 to 160 microns.
- The apparatus and method described in
General Reaction Method 1 above was used to prepare methyl acetate by the carbonylation of dimethyl ether in the presence of Cu-mordenite catalyst (Example 1) and H-mordenite catalyst (Example 2). In Examples 1 and 2 the reaction was allowed to continue for 98 hours under conditions of 300° C., 70 bar, a gas hourly space velocity (GHSV) of 4000 h−1 and with a CO/H2/DME ratio in the total feed of 72/18/10 on a molar basis. After 98 hours each catalyst was subjected to a first regeneration according to the following procedure: - After 98 hours total reaction time the CO/H2/DME feed was switched to N2 and the reactors purged for 30 minutes. The catalysts were then treated at 300° C. and 70 bar total pressure with a gas stream containing 1 volume % O2 (0.7 bar) and 99 volume % N2 for 8 hours at a GHSV of 4000 h−1. After that the oxygen content in the gas stream was increased to 2 volume % (1.4 bar) (with 98 volume % N2) and the catalysts were treated for a further 10 hours at 70 bar total pressure and 300° C.
- After the first regeneration the reactors were purged for 30 minutes with N2. The DME carbonylation reaction was then re-started under conditions of 300° C., 70 bar total pressure, a GHSV of 4000 h−1 with a feedstock ratio of CO/H2/DME 72/18/10. The reaction was then allowed to continue for a further 53 hours (172 hours total) and the CO/H2/DME feed was switched to N2 and the reactors purged for 30 minutes. The catalyst was then subjected to a second regeneration using the same procedure as in the first regeneration.
- After the second regeneration the reactors were purged for 30 minutes with N2. The DME carbonylation reaction was then re-started under conditions of 300° C., 70 bar, a GHSV of 4000 h−1 with a feedstock ratio of CO/H2/DME 72/18/10. The reaction was then allowed to continue for a further 64 hours.
- The results for Examples 1 and 2 are given in
FIGS. 1 and 2 .FIG. 1 shows the initial carbonylation activity of the H-Mordenite catalyst to be fully restored after treatment with 1 volume % (0.7 bar) and 2 volume % (1.4 bar) O2 at 300° C.FIG. 1 also shows the initial carbonylation activity of the Cu(55)-Mordenite catalyst to be largely restored after treatment with 1 and 2 volume % O2 at 300° C. Furthermore, after the initiation period when the DME feed is first introduced to the carbonylation reactor,FIG. 2 shows the initial selectivity of the Cu(55)-Mordenite catalyst to MeOAc (based upon DME converted) to be restored to its original level after regeneration of the catalyst with 1 and 2 volume % (0.7 and 1.4 bar respectively) O2 at 300° C. - A Cu(55) mordenite and H-mordenite prepared as described above were used as the catalyst in Examples 3 and 4 respectively. Each catalyst was used in the carbonylation of dimethyl ether to prepare methyl acetate by the procedure described in
General Reaction Method 1 except that the carbon monoxide, hydrogen, dimethyl ether gas feed had a molar ratio of 76/19/5 and a flow rate of 4 l/h, with a dimethyl ether flow rate of 0.196 l/h (as a vapour) to obtain a CO/H2/DME ratio in the total feed of 76/19/5 on a molar basis. The reaction was allowed to continue for 123 hours under conditions of 300° C., 70 bar total pressure, a GHSV of 4000 h−1 and a CO/H2/DME ratio in the total feed of 76/19/5 on a molar basis. After 129 hours total reaction time, the CO/H2/DME feed was switched to N2 and the reactors purged for 30 minutes. After purging with N2 the temperature of the reactors was dropped to 250° C. and each catalyst was subjected to a first regeneration as follows: - The catalysts were regenerated at 250° C. and 70 bar total pressure with a gas stream containing 1 volume % (0.7 bar) O2 and 99 volume % N2 for 13.5 hours at a GHSV of 4000 h−1. The O2 content in the gas stream was then increased to 2 volume % (1.4 bar) (with 98 volume % N2) and the catalysts were treated for a further 4 hours at 70 bar total pressure and 250° C.
- After the first regeneration the reactors were purged for 30 minutes with N2 and then heated at 3° C./min to 300° C. The carbonylation reaction was then re-started under conditions of 300° C., 70 bar total pressure and a GHSV of 4000 h−1 with a CO/H2/DME molar ratio of 76/19/5. The reaction was allowed to continue for a further 48 hours (197 hours total), after which time, the CO/H2/DME feed was switched to N2 and the reactors purged for 30 minutes. After purging with N2 the temperature of the reactors was dropped to 250° C. and the catalysts were regenerated for a second time by repeating the procedure employed in the first regeneration.
- After the second regeneration the reactors were purged for 30 minutes with N2 and then heated at 3° C./min to 300° C. The carbonylation reaction was re-started under conditions of 300° C., 70 bar, a GHSV of 4000 with a CO/H2/DME molar ratio of 76/19/5. The reaction was allowed to continue for a further 69 hours (287 hours total reaction time) after which time, the CO/H2/DME feed was switched to N2 and the reactors purged for 30 minutes. After purging with N2 the temperature of the reactors was dropped to 250° C. The catalysts were regenerated for a third time by treating the catalysts at 300° C. and 70 bar total pressure with a gas stream containing 1 volume % O2 and 99 volume % N2 for 13.5 hours at a GHSV of 4000 h−1. The O2 content in the gas stream was then increased to 2 volume % (98 volume % N2) and the catalysts were treated for a further 4 hours at 70 bar total pressure, a GHSV of 4000 h−1 and 250° C. The reactors were then heated at 3° C./min to 300° C., and the catalysts treated for a further 6 hours with a gas containing 2 vol % O2 and 98 vol % N2 at a GHSV of 4000 h−1. After the third regeneration the reactors were purged for 30 minutes with N2. The carbonylation reaction was re-started under conditions of 300° C., 70 bar total pressure and a GHSV of 4000 h−1 with a CO/H2/DME molar ratio of 76/19/5. The reaction was allowed to continue for a further 46 hours.
- The results for Examples 3 and 4 are given in
FIG. 3 andFIG. 4 .FIG. 3 shows the initial carbonylation activity of the Cu(55)-Mordenite to be fully restored after 2 regenerations of the catalyst with 1 and 2 volume % O2 at 250° C. Catalyst activity data afterregeneration 3 shown inFIG. 3 also illustrates that after first treating the H-Mordenite catalysts with O2 at 250° C. it is beneficial to further treat the catalyst with O2 at 300° C.FIG. 4 shows that the selectivity of the catalysts after each regeneration is improved compared to the selectivity immediately prior to regeneration. - NH4-mordenite (25.05 g) with a silica to alumina ratio of 20 (ex Zeolyst) was weighed into a 250 mL round bottomed flask with a stirrer bar. 3.2726 g of silver (I) nitrate was dissolved in a minimum amount of deionised water. This solution was then added to the mordenite along with sufficient deionised water (ca. 150 mL) to give a mobile slurry. The top of the flask was covered loosely and the flask stirred overnight. The zeolite was then dried under reduced vacuum using a rotary evaporator before being dried in an oven at 90° C. for 1-2 hours. The zeolite was then calcined in a muffle oven (oven volume=18 L) under a static atmosphere of air at 500° C. for 3 h after two drying stages of 90° C. for 2 hours and 110° C. for 2 hours. The zeolite (ca. 0.75 g batches) was then compacted at 10 tonnes in a 13 mm die set using a pneumatic press, and crushed and sieved to a particle size fraction of 125 to 160 microns. The zeolite (Ag(55)-MOR) had a Ag loading of ca. 55 mole % relative to Al contained in the mordenite. ICP spectroscopic analysis showed the mordenite catalyst to contain 8.2% Ag and 3.6% Al on a % by weight basis, equivalent to a Ag loading of 57 mole % relative to Al.
- Ag-mordenite as prepared above was used as the catalyst in the carbonylation of dimethyl ether to prepare methyl acetate. The method and apparatus of
General Reaction Method 1 was used. The reaction was allowed to continue for 97 hours under conditions of 300° C., 70 bar total pressure, a gas GHSV of 4000 h−1 and with a CO/H2/DME molar ratio in the total feed of 72/18/10. After 97 hours the catalyst was subjected to a first regeneration as follows: - After 97 hours total reaction time the CO/H2/DME feed was switched to N2 and the reactors purged for 30 minutes. After purging with N2 the temperature of the reactors was dropped to 250° C. The catalysts were then treated at 250° C. and 70 bar total pressure with a gas stream containing 1 volume % O2 and 99 volume % N2 for 13.5 hours at a GHSV of 4000 h−1. The O2 content in the gas stream was then increased to 2 volume % (98 volume % N2) and the catalysts were treated for a further 4 hours at 70 bar total pressure and 250° C.
- After the first regeneration the reactors were purged for 30 minutes with N2 and then heated at 3° C./min to 300° C. The carbonylation reaction was re-started under conditions of 300° C., 70 bar total pressure and a GHSV of 4000 h−1 with a CO/H2/DME molar ratio of 72/18/10. The reaction was allowed to continue for a further 50 hours (171 hours total reaction time), after which time the CO/H2/DME feed was switched to N2 and the reactors purged for 30 minutes. After purging with N2 the temperature of the reactors was dropped to 250° C. and the catalyst was subjected to a second regeneration by repeating the method of the first regeneration.
- After the second regeneration the reactors were again purged for 30 minutes with N2 and then heated at 3° C./min to 300° C. The carbonylation reaction was re-started under conditions of 300° C., 70 bar, a GHSV of 4000 h−1 with a CO/H2/DME molar ratio of 72/18/10. The reaction was allowed to continue for a further 71 hours (to a total of 265 hours), after which time the CO/H2/DME feed was switched to N2 and the reactors purged for 30 minutes. After purging with N2 the temperature of the reactors was dropped to 250° C. The catalyst was regenerated for a third time by repeating the method of the first regeneration.
- After the third regeneration the reactors were purged for 30 minutes with N2 and then heated at 3° C./min to 300° C. The carbonylation reaction was re-started under conditions of 300° C., 70 bar, a GHSV of 4000 with a CO/H2/DME molar ratio of 72/18/10. The reaction was allowed to continue for a further 48 hours (to 339 hours total reaction time), after which time, the CO/H2/DME feed was switched to N2 and the reactors purged for 30 minutes. After purging with N2 the temperature of the reactors was dropped to 250° C. and the catalyst was regenerated for a fourth time by repeating the method of the first regeneration.
- After the fourth regeneration the reactors were purged for 30 minutes with N2 and then heated at 3° C./min to 300° C. The carbonylation reaction was re-started under conditions of 300° C., 70 bar, a GHSV of 4000 h−1 with a CO/H2/DME molar ratio of 72/18/10. The reaction was then allowed to continue for a further 69 hours.
- The results for Example 5 are given in
FIGS. 5 and 6 .FIG. 5 shows the initial carbonylation activity of the Ag(55)-Mordenite catalyst to be substantially restored after the first regeneration of the catalyst with 1 and 2 volume % O2 at 250° C.FIG. 6 shows that the selectivity of the catalyst after each regeneration is maintained at or above the selectivity achieved immediately prior to each regeneration. - H-Mordenite (80 g) with a silica to alumina ratio of 20 (ex Süd Chemie) and 14.29 g of copper (II) nitrate hemipentahydrate (98% ACS reagent grade) were weighed into a 500 mL round bottomed flask with a stirrer bar. Sufficient deionised water (ca. 150 mL) was added to the flask to obtain a thick slurry. The top of the flask was loosely covered and the flask left to stir overnight. The zeolite was then dried under reduced vacuum using a rotary evaporator before being dried in an oven at 90° C. for 1 hour. The zeolite was then calcined in a muffle oven (oven volume=18 L) under a static atmosphere of air. The temperature was increased from room temperature to 90° C. at a ramp rate of ca. 3° C./min and then held at this temperature for 2 hours. The temperature was then increased to 110° C. at a ramp rate of ca. 1° C./min and held at this temperature for 2 hours before finally being increased to a temperature of 500° C. at a ramp rate of ca. 3° C./min and held at this temperature for 5 hours. The zeolite was then compacted at 12 tonnes in a 33 mm die set using a Specac Press, and then crushed and sieved to a particle size fraction of 212 to 335 microns. The Cu-mordenite had a Cu loading of 55 mole % of the amount of Al contained in the zeolite.
- Ag-mordenite was prepared by the procedure as described above for the preparation of Cu-mordenite except that the copper (II) nitrate was replaced by 10.47 g of silver nitrate (99% ACS reagent grade). The Ag-mordenite so prepared had a Ag loading of 55 mole % of the amount of Al contained in the mordenite.
- H-Mordenite (80 g) with a silica to alumina ratio of 20 (ex Süd Chemie) was calcined, compacted, crushed and sieved in accordance with the procedures described in the preparation of Cu-mordenite above.
- Each of the catalysts, Cu-mordenite, Ag-mordenite and H-mordenite was used to catalyse the carbonylation of dimethyl ether to methyl acetate using the following apparatus and procedure. The carbonylation reaction was carried out in a pressure flow reactor unit consisting of 60 identical parallel isothermal co-current tubular reactors of the type described in, for example, WO2006107187. The reactors were arranged in 4 blocks of 15 reactors, each block having an independent temperature control. Into each
tube 50 micro litres of catalyst (designed to give a GHSV of 4000 hr−1) was loaded onto a metal sinter having a pore size of 20 micrometers. The catalyst samples were heated at a ramp rate of 5° C./min. to 100° C. at atmospheric pressure under 98.6 mole % nitrogen and 1.4 mole % helium at a flow rate of 3.4 mL/min, and held at this temperature for 1 hour. The reactor was then pressurised to 70 barg with a gas mixture comprising 98.6 mole % nitrogen and 1.4 mole % helium and the system held at this condition for 1 hour. The gas feed was then changed from the nitrogen and helium mix to a mixture comprising 63.1 mole % carbon monoxide, 15.8 mole % hydrogen, 19.7 mole % nitrogen and 1.4 mole % helium at a gas flow rate of 3.4 mL/min, and the reactors were heated at aramp rate 3° C./min. to a temperature of 300° C. The system was then held at this condition for 3 hours. At this point catalyst activation is considered complete, and the gas feed was changed to a mixture comprising 63.1 mole % carbon monoxide, 15.8 mole % hydrogen, 14.8 mole % nitrogen, 1.4 mole % helium and 4.9 mole % dimethyl ether at a gas flow rate of 3.4 mV min. The reaction was allowed to continue for 161.2 hours at which stage the gas feed was changed to mixture comprising 98.6 mole nitrogen and 1.4 mole % helium at a gas flow rate of 3.4 ml/min, and all of the reactors were allowed to cool down to 100° C. The system was held under these conditions for 30 minutes and then regeneration of the catalysts was conducted under the conditions in the following table. In all cases the gas flow was 3.4 ml/min at a pressure of 70 barg. -
Block Nitrogen Air* Helium 1 deg Block 2 Block 3Block 4Time mole % mole % mole % C. deg C. deg C. deg C. hours 78.9 19.7 1.4 250 300 350 400 5.8 59.2 39.4 1.4 250 300 350 400 5.8 19.7 78.9 1.4 250 300 350 400 5.8 *Air = 20.95 mol % oxygen, 78.05 mol % nitrogen and 1 mol % other gases, mostly argon. - Once this was complete, the gas feed was changed to a mixture comprising 98.6 mole % nitrogen and 1.4% helium and the reactor were allowed to cool down to 100° C. The system was held at this condition for 30 minutes before the reactors were heated to 300° C. and the gas feed changed to a mixture comprising 63.1 mole % carbon monoxide, 15.8 mole % hydrogen, 19.7 mole % nitrogen and 1.4 mole % helium at a gas flow rate of 3.4 mL/min. The system was held at this condition for 3 hours before the carbonylation reaction was re-started by changing the feed to a mixture comprising 63.1 mole % carbon monoxide, 15.8 mole % hydrogen, 14.8 mole % nitrogen, 1.4 mole % helium and 4.9 mole % dimethyl ether. The exit stream from the reactor was passed to two gas chromatographs. One of these was a Varian 4900 micro GC with three columns (Molecular sieve 5A, Porapak® Q, and CP-Wax-52) each quipped with a thermal conductivity detector. The other was an Interscience Trace GC with two columns (CP-
Sil 5 and CP-Wax 52) each equipped with a flame ionisation detector. The STY to Acetyls products (g/l/h) is shown inFIG. 7 and Selectivity to Acetyls products is shown inFIGS. 8 to 10 . Selectivity is defined as the molar selectivity of the reaction of the methoxy group in the dimethyl ether (DME) feed to the products acetic acid (AcOH) and methyl acetate (MeOAc). -
Selectivity=([MeOAc]out+[AcOH]out)/([DME]in−[DME]out−0.5*[MeOH]out−0.5*[MeOAc]out)*100 -
FIG. 7 shows that the activity of the Cu-mordenite catalyst is restored after regeneration. -
FIG. 8 shows that shortly after regeneration at 250 and 300° C. the selectivity of Cu-mordenite catalyst has been substantially restored to the selectivity achieved immediately prior to regeneration. In comparison the selectivity of Cu-mordenite regenerated at 350 and 400° C. has been dramatically reduced, and even though the selectivity of the catalyst regenerated at 350° C. is recovering it is still not within 10% of the selectivity of the catalyst prior to the regeneration treatment after over 60 hours of operation. -
FIG. 9 shows that regeneration at 350° C. and 400° C. adversely affects the selectivity of the Ag-mordenite catalyst andFIG. 10 shows that regeneration at 400° C. adversely affects the selectivity of the H-mordenite catalyst.
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BR112015017280A2 (en) | 2013-01-21 | 2017-07-11 | Bp Chem Int Ltd | process for treating zeolite catalysts |
US10512902B2 (en) * | 2015-12-18 | 2019-12-24 | Bp Chemicals Limited | Carbonylation process using a pretreated zeolite catalyst |
CN106890669B (en) * | 2015-12-18 | 2019-04-02 | 中国科学院大连化学物理研究所 | A kind of catalyst producing methyl acetate, preparation method and application |
CN108579794A (en) * | 2018-04-02 | 2018-09-28 | 新疆大学 | The molecular sieve catalyst of gold-supported is used to convert the method that methanol is methyl acetate |
CN112250573B (en) * | 2020-10-20 | 2021-08-17 | 西南化工研究设计院有限公司 | Method for preparing methyl acetate by dimethyl ether carbonylation |
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GB9223170D0 (en) | 1992-11-05 | 1992-12-16 | British Petroleum Co Plc | Process for preparing carboxylic acids |
US5648585A (en) * | 1993-12-29 | 1997-07-15 | Murray; Brendan Dermot | Process for isomerizing linear olefins to isoolefins |
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DE10361003B3 (en) | 2003-12-23 | 2005-07-28 | Hte Ag The High Throughput Experimentation Company | Apparatus and method for pressure and flow control in parallel reactors |
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US20060252959A1 (en) | 2005-05-05 | 2006-11-09 | The Regents Of The University Of California | Process for carbonylation of alkyl ethers |
GB0607394D0 (en) * | 2006-04-12 | 2006-05-24 | Bp Chem Int Ltd | Process |
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US5196621A (en) * | 1991-04-19 | 1993-03-23 | The Dow Chemical Company | Process for the cyclodimerization of 1,3-butadienes to 4-vinylcyclohexenes |
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CN110013886A (en) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | Catalyst situ regeneration device |
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TWI450884B (en) | 2014-09-01 |
EP2072124A1 (en) | 2009-06-24 |
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CN101903100B (en) | 2012-11-07 |
CN101903100A (en) | 2010-12-01 |
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US8158815B2 (en) | 2012-04-17 |
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WO2009077745A1 (en) | 2009-06-25 |
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